Method for synthesis of copper/copper oxide nanocrystals

Patent metadata

Field	Value
Publication number	US-10913056-B2
Application number	US-201715664795-A
Country	US
Kind code	B2
Filing date	Jul 31, 2017
Priority date	Jul 31, 2017
Publication date	Feb 9, 2021
Grant date	Feb 9, 2021

Abstract

A simple approach to produce mixed Cu/Cu2O nanocrystals having a specific morphology by controlling the reaction temperature during Cu/Cu2O nanocrystals synthesis. Other variables are kept constant, such as the amount of reactants, while the reaction temperatures is maintained at a predetermined temperature of 70° C., 30° C. or 0° C., which are used to produce different and controlled morphologies for the Cu/Cu2O nanocrystals. The reaction mixture includes a copper ion contributor, a capping agent, a pH adjustor, and reducing agent. The reaction mixture is held at the predetermined temperature for three hours to produce the Cu/Cu2O nanocrystals. The synthesis method has advantages such as mass production, easy operation, and high reproducibility.

First claim

The invention claimed is:

1. A method of producing Cu 2 O/Cu nanocrystals, comprising:
providing a solution including a copper ion contributor and a capping agent dissolved in a solvent;
adding a reducing agent to the solution to thereby form a reaction mixture; and
reacting the reaction mixture at a predetermined temperature to thereby precipitate Cu 2 O/Cu nanocrystals from the reaction mixture;
wherein the predetermined temperature is from 65° C. to 75° C., from 25° C. to 35° C., or from −5° C. to 5° C.;
wherein a molar ratio of the capping agent to the copper ion contributor is 0.0005-0.08 in the reaction mixture.

2. The method according to claim 1 , wherein the solvent comprises water, aqueous ammonia solutions, an organic solvent, or combinations thereof.

3. The method according to claim 2 , wherein the solvent is deionized water.

4. The method according to claim 1 , wherein the copper ion contributor comprises copper (II) chloride (CuCl 2 ), copper (II) fluoride (CuF 2 ), copper (II) bromide (CuBr 2 ), copper (II) iodide (CuI 2 ), cuprous iodide (CuI), copper (II) oxide (CuO), copper (II) sulfide (CuS), copper (II) sulfate (CuSO 4 ), copper (II) nitride (Cu 3 N 2 ), copper(II) nitrate (Cu(NO 3 ) 2 ), copper (II) phosphide (Cu 3 P 2 ), copper(II) acetate (Cu(CH 2 CO 2 − )), copper (II) hydroxide (CuOH) 2 , copper(II) carbonate (CuCO 3 ), copper(II) acetylacetonate (Cu(C 5 H 7 O 2 ) 2 ), a hydrate thereof, or combinations thereof.

5. The method according to claim 4 , wherein the copper ion contributor is copper (II) chloride dihydrate, and the copper (II) chloride dihydrate is included at a molar concentration of 5-15 mM.

6. The method according to claim 1 , wherein the capping agent comprises polyvinylpyrrolidone, plant-derived extracts, ethylene glycol, oleic acid, sodium laureth sulfate, sodium metaphosphate, oleylamine, dodecylbenzenesulfonic acid, ethylene diamine, triphenylphosphine oxide, peracetic acid, polyethylene glycol, fructose, tetramethylammonium hydroxide, amino acids, or combinations thereof.

7. The method according to claim 6 , wherein the capping agent is polyvinylpyrrolidone with an average molecular weight of 30,000-50,000 g/mol, and the polyvinylpyrrolidone is included at a molar concentration of 0.01-0.08 mM.

8. The method according to claim 1 , wherein the reducing agent comprises L-ascorbic acid, hydrazine monohydrate, sodium borohydride, hydrazine, 1,2-hexadecanediol, glucose, carbon monoxide, sulfur dioxide, iodides, hydrogen peroxide, oxalic acid, formic acid, carbon, reducing sugars, a borane compound, or combinations thereof.

9. The method according to claim 8 , wherein the reducing agent is L-ascorbic acid, and the L-ascorbic acid is included at a molar concentration of 0.01-0.1 M.

10. The method according to claim 1 , further comprising adding a pH adjuster to the reaction mixture to adjust the pH of the reaction mixture to be between 2.0 and 12.0.

11. The method according to claim 10 , wherein the pH adjuster is sodium hydroxide, and the sodium hydroxide is included at a molar concentration of 0.005-0.04 M.

12. A method of producing Cu 2 O/Cu nanocrystals, comprising:
providing a solution including a copper ion contributor and a capping agent dissolved in a solvent;
adding a reducing agent to the solution to thereby form a reaction mixture;
determining a desired morphology for the Cu 2 O/Cu nanocrystals from among 820 nm±50 nm corner truncated cubes, 220 nm±20 nm slightly corner truncated cubes, and 400 nm±30 nm slightly corner truncated cubes;
if the desired morphology is 820 nm±50 nm corner truncated cubes, then reacting the reaction mixture at a temperature of 65° C. to 75° C. to thereby precipitate Cu 2 O/Cu nanocrystals with the desired morphology from the reaction mixture;
if the desired morphology is 220 nm±20 nm slightly corner truncated cubes, then reacting the reaction mixture at a temperature of 25° C. to 35° C. to thereby precipitate Cu 2 O/Cu nanocrystals with the desired morphology from the reaction mixture; and
if the desired morphology is 400 nm±30 nm is slightly corner truncated cubes, then reacting the reaction mixture at a temperature of −5° C. to 5° C. to thereby precipitate Cu 2 O/Cu nanocrystals with the desired morphology from the reaction mixture.

13. The method according to claim 12 , wherein a ratio of the capping agent to the copper ion contributor is 0.0005-0.08.

14. The method according to claim 12 , wherein the copper ion contributor comprises copper (II) chloride dihydrate, and the copper (II) chloride dihydrate is included at a molar concentration of 5-15 mM.

15. The method according to claim 12 , wherein the capping agent comprises polyvinylpyrrolidone, plant-derived extracts, ethylene glycol, oleic acid, sodium laureth sulfate, sodium metaphosphate, oleylamine, dodecylbenzenesulfonic acid, ethylene diamine, triphenylphosphine oxide, peracetic acid, polyethylene glycol, fructose, tetramethylammonium hydroxide, amino acids, or combinations thereof.

16. The method according to claim 15 , wherein the capping agent is polyvinylpyrrolidone with an average molecular weight of 30,000-50,000 g/mol, and the polyvinylpyrrolidone is included at a molar concentration of 0.01-0.08 mM.

17. The method according to claim 12 , wherein the reducing agent comprises L-ascorbic acid, hydrazine monohydrate, sodium borohydride, hydrazine, 1,2-hexadecanediol, glucose, carbon monoxide, sulfur dioxide, iodides, hydrogen peroxide, oxalic acid, formic acid, carbon, reducing sugars, a borane compound, or combinations thereof.

18. The method according to claim 12 , further comprising adding sodium hydroxide to the reaction mixture to adjust the pH of the reaction mixture to be between 2.0 and 12.0; wherein the sodium hydroxide is included at a molar concentration of 0.005-0.04 M.

19. The method according to claim 18 , wherein the reducing agent is L-ascorbic acid, and the L-ascorbic acid is included at a molar concentration of 0.01-0.1 M.

20. A method of producing Cu 2 O/Cu nanocrystals, comprising:
providing a solution including a copper ion contributor and a capping agent dissolved in a solvent;
adding a reducing agent to the solution to thereby form a reaction mixture; and
reacting the reaction mixture at a predetermined temperature to thereby precipitate Cu 2 O/Cu nanocrystals from the reaction mixture;
wherein the predetermined temperature is from 65° C. to 75° C., from 25° C. to 35° C., or from −5° C. to 5° C.; and
wherein the copper ion contributor is copper (II) chloride dihydrate, and the copper (II) chloride dihydrate is included at a molar concentration of 5-15 mM.

21. A method of producing Cu 2 O/Cu nanocrystals, comprising:
providing a solution including a copper ion contributor and a capping agent dissolved in a solvent;
adding a reducing agent to the solution to thereby form a reaction mixture; and
reacting the reaction mixture at a predetermined temperature to thereby precipitate Cu 2 O/Cu nanocrystals from the reaction mixture;
wherein the predetermined temperature is from 65° C. to 75° C., from 25° C. to 35° C., or from −5° C. to 5° C.; and
wherein the capping agent comprises polyvinylpyrrolidone, plant-derived extracts, ethylene glycol, oleic acid, sodium laureth sulfate, sodium metaphosphate, oleylamine, dodecylbenzenesulfonic acid, ethylene diamine, triphenylphosphine oxide, peracetic acid, polyethylene glycol, fructose, tetramethylammonium hydroxide, amino acids, or combinations thereof.

22. A met

Assignees

• Honda Motor Co Ltd
• Univ Temple
• Temple Univ Of The Commonwealth System Of Hi

Inventors

• Chen Gugang
• Harutyunyan Avetik
• Rao Yi
• Li Xia

Classifications

• C01G3/02 Primary

  Oxides; Hydroxides · CPC title

• C01P2004/38

  cube-like · CPC title

• C01P2004/80

  Particles consisting of a mixture of two or more inorganic phases · CPC title

• C01P2002/72

  by d-values or two theta-values, e.g. as X-ray diagram · CPC title

• C01P2004/62

  Submicrometer sized, i.e. from 0.1-1 micrometer · CPC title